EP0707620B1 - Festschmierstoff und beschichtungssystem aus härtbarem stahl - Google Patents

Festschmierstoff und beschichtungssystem aus härtbarem stahl Download PDF

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Publication number
EP0707620B1
EP0707620B1 EP94918927A EP94918927A EP0707620B1 EP 0707620 B1 EP0707620 B1 EP 0707620B1 EP 94918927 A EP94918927 A EP 94918927A EP 94918927 A EP94918927 A EP 94918927A EP 0707620 B1 EP0707620 B1 EP 0707620B1
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Prior art keywords
particles
solid lubricant
grains
coating
coating system
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EP94918927A
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English (en)
French (fr)
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EP0707620A1 (de
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V. Durga Nageswar Rao
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Ford Werke GmbH
Ford France SA
Ford Motor Co Ltd
Ford Motor Co
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Ford Werke GmbH
Ford France SA
Ford Motor Co Ltd
Ford Motor Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0221—Using a mixture of prealloyed powders or a master alloy comprising S or a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • B23K35/327—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C comprising refractory compounds, e.g. carbides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component

Definitions

  • This invention relates to the art of fluid lubricated metal wear interfaces or contacts, and more particularly to the use of anti-friction solid film lubricants for such interfaces modified to withstand high unit scraping or bearing loads at high temperatures while functioning with either full or partial wet lubrication.
  • U.S. patent 1,654,509 (1927) discloses use of powder graphite trapped or covered by a metal binder (i.e., iron, aluminium, bronze, tin, lead, babbitt, or copper) to form a thick coating; the metal is heated to at least a thermoplastic condition by melting or arc spraying to bury the graphite.
  • a metal binder i.e., iron, aluminium, bronze, tin, lead, babbitt, or copper
  • the coating offers limited friction reducing characteristics.
  • EP-A 0 487 273 discloses a thermal spray powder for the production of abradable seals, e.g. for rotating parts of axial flow gas turbines, comprising an agglomerate of a matrix-forming component (e.g. a metal), a solid lubricant (e.g. a fluoride or boron nitride) and a plastic, which normally remains as part of the coating.
  • a matrix-forming component e.g. a metal
  • a solid lubricant e.g. a fluoride or boron nitride
  • the inventor of the present invention has previously disclosed certain solid lubricants operable at high temperatures, but designed for either interfacing with ceramics, not metals, and generally at low load applications in the absence of any liquids, or with metals in an oilless environment.
  • One solid film lubricant disclosed comprises graphite and boron nitride in a highly viscous thermoplastic polymer binder spread in a generous volume onto a seal support comprised of nickel and chromium alloy.
  • the formulation was designed to provide a hard coating which softens at the surface under the load, while at or above the operating temperature and while functioning only under dry conditions.
  • Thermoplastic polymer based formulations are unsatisfactory, unless substantially modified, in meeting the needs of a highly loaded engine component, such as a cylinder bore, because the interfacing surfaces are subject to wet lubrication, the unit loads are significantly higher (approaching 3.5 MPa (500 psi)) and the surface temperatures are far higher, causing scraping.
  • Another solid film lubricant disclosed was halide salts or MoS 2 (but not as a combination) in a nickel, copper, or cobalt binder; the coating, without modifications, would not be effective in providing a stable and durable anti-friction coating for the walls of an internal combustion cylinder bore, because the formulations were designed to operate under dry conditions and against ceramics (primarily lithium aluminium silicate and magnesium aluminium silicate), and thus the right matrix was not used, nor was the right combination of solid film lubricants used.
  • formulations were designed to produce a ceramic compatible oxide (e.g., copper oxide or nickel oxide) through partial oxidation of the metal in the formulation. These systems were also designed to also permit as much as 300-500 microns of wear. For cylinder bore lubrication, only 5-10 microns of wear is tolerated.
  • a ceramic compatible oxide e.g., copper oxide or nickel oxide
  • Such a coating system in accordance with the invention, is set forth in claim 1, and can economically reduce friction for high temperature applications, particularly along a cylinder bore wall at temperatures above 315°C (600°F) when oil lubrication fails or in the presence of oil flooding (while successfully resisting conventional or improved piston ring applied loads).
  • a method according to the invention provides a low cost method of making coated cylinder walls by rapidly applying a coating by plasma spraying at reduced or selected areas of the bore wall while achieving excellent adherence and precise deposition, the method demanding less rough and finish machining of the final bore surface.
  • An aluminium alloy cylinder wall of an engine which is coated with a coating composition embodying the invention has advantages that it (i) assists in achieving reduced piston system friction and reduced piston blow-by, all resulting in an improved vehicle fuel economy of 2-4% for a gasoline powered vehicle; (ii) reduces hydrocarbon emissions; and (iii) reduces engine vibration by at least 20% at wide-open throttle conditions at moderate speeds (i.e. 1000-3000 rpm).
  • the coating system comprises agglomerates of particles forming grains adhered to a metal substrate or interface, said particles being comprised of (i) particles of at least two solid lubricant particles selected from the group consisting of graphite, hexagonal boron nitride, molybdenum disulfide, lithium fluoride, calcium fluoride, and eutectic mixtures of LiF/CaF 2 or LiF/NaF; and (ii) steel particles fused together and bounding said solid lubricant particles at least at certain intersections, certain portions of said steel particles being air-hardened to a high hardness upon exposure of the coating to the interface at high temperatures.
  • the steel particles be of a stainless steel character consisting preferably of 70% iron, 15-24% chromium, and about 8% nickel.
  • the agglomerates preferably comprise by volume: 15-25% solid lubricant particles and 74-84% stainless steel particles.
  • the air-hardened hardness of the steel is about Rc 60, and the coefficient of friction achieved by the coating system is about .14 dry and 0.06-0.08 under partially wet lubricated conditions.
  • anti-friction coated surfaces subject to sliding wear are made by the steps of (a) forming grains of agglomerated particles of at least two oil-attracting solid lubricants selected from the group consisting of graphite, molybdenum disulfide, boron nitride, calcium fluoride, sodium fluoride and lithium fluoride, and of air-hardenable, fusable ingredients such as steel particles, the particles being agglomerated by a low melting, easily combustible, ash-free binder or medium such as wax; (b) providing a light metal-based component surface; (c) thermally spraying such grains onto said surface in a thickness range of 100-250 microns to form a coating substantially devoid of the binder (the temperature of said thermal spraying eliminating the wax by ash-free combustion) ; (d) removing at least a portion of the fusable particles by honing to expose edges of such particles; and (e) subjecting the exposed particles to air hardening
  • the invention also provides an engine block with one or more anti-friction coated cylinder bores.
  • the block comprises: (a) a cast aluminium based cylinder block having at least one cylinder bore wall; (b) an oil-attracting coating of grains fused to each other and to said bore wall, said grains comprising agglomerates of particles of at least two oil-attracting solid lubricants and hardened, fused particles, the solid lubricant particles being selected from the group consisting of graphite molybdenum disulfide, boron nitride, lithium fluoride, calcium fluoride, and eutectic mixtures of LiF/CaF 2 or LiF/NaF, the coating having been finish-honed to expose certain margins of the fused particles.
  • the coating system cannot rely on graphite or any one lubricant by itself, but rather upon a specific combination of solid lubricants entrained in an air-hardenable metallic framework that, when honed to a smooth interfacing surface, will function as wear-resistant, anti-friction bearing surfaces.
  • the inventive system comprises a layer A of powder grains adhered to a metal substrate or wall 10, each grain containing an agglomeration 11 of oil-attracting solid lubricant particles and air-hardenable, fusable ingredients surrounding each of the solid lubricant particles.
  • the oil-attracting solid lubricant particles are selected from the group consisting of graphite, molybdenum disulfide, boron nitride, calcium difluoride, lithium fluoride, and eutectic mixtures of LiF/CaF 2 or LiF/NaF.
  • the fusable air-hardenable ingredients are preferably a stainless steel consisting of about 4-24% chromium, 6-12% nickel when used, 4-6% manganese when used, 0-4% Al, and the remainder iron.
  • the solid lubricants are stable at 315-425°C (600-800°F) and give the coating high temperature stability for use in the cylinder bores of internal combustion engines.
  • the grains adhere to the substrate as a result of fusion when the shells 12 of the fusable particles are softened as a result of thermal spraying.
  • the unfused portion 13 of the air-hardenable particles provides an encapsulation in part for the solid lubricant-containing core.
  • the powder useful as a raw material in creating the coating system, is comprised of powder grains 14, such as shown in Figure 2, which are agglomerates 11 of solid lubricant particles 15, here being boron nitride 15a, molybdenum disulfide 15b, graphite 15c, calcium difluoride 15d, and lithium fluoride 15e.
  • solid lubricant particles are interspersed with air-hardenable steel particles 16 which are held together by a low melting medium or binder, such as wax, 17.
  • the steel particles are selected from iron alloys containing (i) 8-20% chromium and 1-4% aluminium; (ii) 4-20% chromium, 4-6% Mn, and 6-12% Ni; and (iii) stainless steel having 15-24% Cr, and 8% nickel.
  • the wax binder can be a wax having the following composition: 0.5-2.0% conventional carbowax, gum arabic, and poly vinyl alcohol.
  • the solid lubricant particles preferably have a size in the range of 5-40 microns; the steel particles have a starting average particle size in the range of 20-50 microns.
  • the agglomerated particles (in the wax binder) form grains having a size in the range of 40-55 microns.
  • Such particle and grain size ranges are important because they make possible a flowable powder useful in the thermal spray deposition process.
  • the size is substantially below 40 microns, the powder will not flow freely; when significantly above 55 microns, stratification of the different particles will occur.
  • the particles of solid lubricant desirably should be in a proportion of 15-25% of each grain with the steel particles being 74-84% by volume, the wax binder constituting less than 4% of the grains. However, the wax binder burns off during thermal spraying.
  • the solid lubricant particles 15 may be encapsulated within a metal shell 18 prior to agglomeration by wax; shell metal or metal alloy is selected from the group consisting of nickel, copper, iron, and cobalt.
  • shell metal or metal alloy is selected from the group consisting of nickel, copper, iron, and cobalt.
  • Such encapsulated particles are created by a prior treatment wherein solid lubricants are placed in a molten bath of the metal and stirred, and then the slurry is comminuted so as to form the encapsulated lubricant particles 20 ( Figure 3a).
  • the steel particles 16 may be encapsulated in the same type of shell 18 by a similar process to form a particle 21 (see Figure 3b).
  • the metal encapsulation may be provided by hydrometallurgy whereby solid film lubricant particles are suspended in a solution of the easily decomposed salt of the metal at higher temperatures and pressure, the metal deposits on the surface of the particles.
  • the encapsulated particles then are bound together by the wax 17 to form the grains as previously discussed (see Figure 3).
  • Other hard particles 19 may be incorporated along with the encapsulated particles.
  • the optional hard particles or encapsulated particles facilitate harder bearing surfaces or silts uniformly distributed throughout the coating.
  • the powder may be made alternatively by spray drying; to this end, a water-based slurry of very fine particles is prepared (the particles are solid lubricants and soft metals (Ni, Co, etc.).
  • the slurry is blended with .5-1.5% by weight water soluble organic binder such as gum arabic and/or polyvinyl alcohol or carbowax.
  • the blended slurry is then atomised into a hot circulating air chamber at or about 150°C (300°F).
  • the preferred coating when operatively used, will have a glazed or polished outer surface 60 as a result of engine start-up use and will have edges 61 of the steel particle network 62 exposed as a result of honing to function much like needle bearings within the coating.
  • the coating has a significantly useful porosity 23 which retains fluid oil for additional lubrication.
  • Friction in an oil-bathed environment will be dependent partly upon fluid friction and the oil film (layers in the fluid sheared at different velocities, commonly referred to as hydrodynamic friction), and, more importantly, dependent on dry or coulomb friction between contacting solid, rigid bodies (also referred to as boundary friction). Dry friction is tangential and opposed to the direction of sliding interengagement. As shown in Figure 5, there is a visualisation of the mechanical action of friction. The weight of a block (or applied load) imposes a normal force N on table C that is spread across several load forces N-1 at each interengaging hump 22 (see Figure 6). The composite of all the tangential components of the small reaction forces F-1 at each of the interengaged humps 22 is the total friction force F.
  • the humps are the inherent irregularities or asperities in any surface on a microscopic scale.
  • the contacts are more nearly along the tops of the humps and therefore the tangential reaction forces will be smaller.
  • the coefficient of friction will be greater. Friction is influenced by the deformation and tearing of surface irregularities, hardness of the interengaged surfaces, and the presence of surface film such as oxides or oils. As a result, actual friction will be different from idealised perfect contact friction and will depend upon the ratio between shear and yield stresses of the interengaged surfaces.
  • the presence of a film on each of the interengaging surfaces (see Figure 7) will serve to change the coefficient of friction depending upon the shear and yield stress capacities of the films and their relative hardness.
  • Friction is also influenced significantly by temperature because high local temperatures can influence adhesion at the contact points.
  • the critical stress for slip goes down, exposing more surface to sliding and thereby increasing friction.
  • the hardness (E) goes down, resulting in galling and scuffing. This is accounted for in the friction equation: f ⁇ 1/(Ts-T), Ts being the surface temperature and T being the bulk temperature of the sliding part.
  • the influence of temperature is particularly evident on graphite as shown in Figure 10.
  • the coefficient of friction for block graphite rapidly increases to above .4 at 260°C (500°F) and above .5 at 425°C (800°F), and even higher at 540°C (1000°F).
  • the coefficient of friction for graphite at 205°C (400°F) or lower becomes generally uniform at below .05. Contrast this with the coefficient of friction performance and wear performance of the coating system containing both graphite and boron nitride represented in Figure 11.
  • the coating for Figure 11 comprises only particles of graphite, boron nitride, and a thermoset polymer.
  • At least two different solid lubricant particles must be present in the powder grains.
  • Graphite when selected, should be present in an amount of 20-70% by weight of the solid lubricants.
  • Graphite as earlier indicated, is effective as a solid lubricant only up to temperatures around 205°C (400°F) and possesses very poor load bearing capability such as that experienced by a piston ring scraping against the graphite itself.
  • Molybdenum disulfide when selected, should be present in an amount of 20-70% by weight of the solid lubricants, and, most importantly, is effective in increasing the load bearing capability as well as the temperature of low friction stability of the mixture up to a temperature of at least 305°C (580°F), but will break down into molybdenum and sulfur at temperatures in excess of 305°C (580°F) in air or nonreducing atmospheres.
  • Molybdenum disulfide reduces friction in the absence of oil or in the presence of oil, and, most importantly, supports loads of at least 70 kPa (10 psi) at such high temperatures.
  • Molybdenum disulfide is also an oil attractor and is very useful in this invention.
  • Boron nitride when selected, should be present in an amount of 5-40% by weight of the solid lubricants, and increases the stability of the mixture up to temperatures as high as 700°F and concurrently stabilises the low friction temperature limit for the ingredients of molybdenum disulfide and graphite. Boron nitride is also an effective oil attractor. Calcium difluoride and lithium fluoride are oil attractors, and are stable up to temperatures of 815°C (1500°F) and 650°C (1200°F), respectively, and resist loads of at least 70 kPa (10 psi).
  • the coating A must be porous, having a pore volume 23 of about 2-10%, as shown in Figure 4.
  • Porosity allows fluid oil to be retained in the pores of the coating as an impregnant during operation of the engine.
  • temperature stability is important because typical engine cylinder bore wall will experience, at certain zones thereof and under certain engine operating conditions such as failure of coolant or oil pump), temperatures as high as 370°C (700°F) even though the hottest zone of the cylinder bore surface in the combustion chamber, during normal operation, is only about 540°F.
  • the optimum mixture contains all of such solid lubricant ingredients, which will provide for a temperature, stability up to temperatures as high as 425°C (800°F), load bearing capacities of at least 70 kPa (10 psi), and excellent oil attraction capability.
  • the coefficient of friction for the grains in the deposited condition will be in the range of .07-.08 at room temperature, and a coefficient of friction as low as .03 at 370°C (700°F).
  • the comprehensive method of making coated surfaces such as cylinder bore walls comprises the series of steps: (a) forming grains of agglomerated particles, the particles including solid lubricants and air-hardenable metals; (b) providing a light metal or light metal alloy surface, the metal being selected from the group of aluminium, magnesium, silicon, and titanium; (c) thermally spraying the agglomerated particles onto the surface, the cylinder surface may be the parent bore surface of a cylinder block; (d) honing the sprayed coating on the surface to a predetermined thickness and smoothness to expose edges of the metallic fused network of the coating as well as smear the solid lubricants across the honed surface; and (e) subjecting the honed coating to frictional use to harden at least some portion of the metallic content of the grains of the coating.
  • Plasma sprayed powder will form a controlled porosity that allows for impregnation of wet oil;
  • the encapsulated powder grains create asperities in the surface such that, when honed, the edges of the shell metal provide a smaller localised area of hard supporting asperities where boundary layer shear will take place in the smeared solid lubricant thereover to further reduce friction (similar to microgrooving); and
  • the liner 14 would preferably be constituted of the same material as that of the parent bore surface 15.
  • the liner can be any metal that has a higher strength than the metal of the parent bore wall; this is often achieved by making an alloy of the metal used for the parent bore wall.
  • C-355 or C-356 aluminium alloys for the liner are stronger than the 319 aluminium alloy commonly used for aluminium engine blocks.
  • the liner must have, generally, thermal conductivity and thermal expansion characteristics essentially the same as the block.
  • the liner is coated interiorly at 18, as will be described subsequently, and the liner then assembled to the parent bore by either being frozen to about a temperature of -40°C (-40°F) while maintaining the parent bore at room temperature, or the parent bore may be heated to 130°C (270°F) while the liner is retained at room temperature.
  • a shrink-fit is obtained by placing the liner in such differential temperature condition within the parent bore 15.
  • the liner is coated at 17 on its exterior surface 16 with a copper flake epoxy mixture (70-90% copper flake), the epoxy being of the type described for use in coating.
  • the copper flake within such epoxy coating assures not only an extremely solid bond between the liner and the light metal parent bore, but also increases the thermal transfer therebetween on a microscopic scale.
  • the liner may also be cast-in-place when the block or bore wall is being formed; such liner would then be treated as the parent bore surface.
  • the liner can also be made from the solid film lubricants and air-hardenable metal powder composition and formed into a liner shape by conventional powder metal forming and sintering techniques.
  • Plasma spraying of a flowable powder is carried out to form an adherent porous layer of powder grains on the bore wall or surface, the powder consisting of particles of at least two solid lubricants selected from the group of graphite, molybdenum disulfide, boron nitride, calcium difluoride, and lithium fluoride.
  • the flowable powder can be and often is a composite of the solid film lubricant and the soft metal powder produced by spray drying in which a combustible, ash-free, organic binder (such as 1% carbowax) and/or 0.5% gum arabic are used to produce the slurry from which the spray-dried powder is produced.
  • the coating is also subjected to high temperature frictional use to harden at least a portion of the metallic contents of the grains.
  • the segment 25 would desirably be undercut to receive the thermally sprayed coating in a thickness that fills at least the undercut. Then, on honing simultaneously both the filled undercut and aligned bore wall, a smooth surface for the piston rings is created.
  • Plasma spraying may be carried out by equipment, as illustrated in Figure 15, which uses a spray gun 30 having a pair of interior electrodes 30a and 30b that create an arc through which powdered metal and inert gas are introduced to form a plasma.
  • the powder may be introduced through a supply line 31 connected to a slip ring 32 that in turn connects to a powder channel 33 that delivers to the nozzle 34.
  • the plasma heats the powder, being carried therewith, along the shells of the powder only.
  • the gun is carried on an articulating arm 35 which is moved in a combined circular linear movement by a journal 36 carried on an eccentric positioner 37 which in turn is carried on a rotating disc 38 moved by motor 39.
  • Variations of the plasma spray coating can be obtained by mixing particles consisting of nickel or cobalt encapsulating solid lubricants along with hard particles such as ferro-chrome or ferro-manganese.
  • the hard particles will produce a very hard matrix deposit due to the interaction alloying with nickel in the hot plasma flame to create intermetallics. This is a very desirable condition for decreased wear without any increase in friction. In such cases, only a very thin upper solid film lubricant coating is needed.
  • the thickness of the coating should be controlled to about 120-140 microns allowing for the subsequent removal of about 100 microns by honing. Honing should be carried out by conventional honing stones to not affect the chemistry of the coating.
  • the coating is subjected to high temperature frictional use, such as engine usage itself, whereby combustion gases and the frictional scraping of the piston rings subjects the exposed portions of the coating to heat and pressure that causes hardening to take place within the exposed steel itself. It is the carbon in FeCr and in the solid film lubricant that makes such hardening possible.
  • the hardness conversion can be explained as follows: the fused particle, as it cools through melting and solidifying, will form an air-hardenable steel composition such as Hadfield manganese steel.
  • the product is an engine block with at least one anti-friction coated cylinder bore.
  • the product comprises: (a) a cast aluminium alloy based cylinder block having at least one cylinder bore wall; (b) a hard, load-supporting face on the wall; and (c) a mixture adherent on said face, which mixture comprises oil-attracting solid lubricant particles and fused, air-hardened steel particles, the mixture supporting loads of at least 70 kPa (10 psi) at temperatures of 315-425°C (600-800°F) while being stable at such temperatures, the mixture having at least two elements selected from the group consisting of graphite, molybdenum disulfide, boron nitride, calcium difluoride, sodium fluoride, and lithium fluoride.
  • Such product is characterized by a reduction in engine friction resulting from reduction of piston system friction of at least 25% because of the ability to operate the engine with near zero piston/cylinder bore clearance as well as a reduction in mechanical boundary friction. Furthermore, such product provides for reduction in the hydrocarbon emissions from the engine by at least 25% because of the adaptation of the piston ring designs disclosed in concurrently filed patent applications and thereby reduce the top land crevice volume. The blow-by of the engine (combustion gases blowing past the piston rings) is reduced also by 25% because of the near zero clearance combined with the piston ring design just cited. Furthermore, the temperature of the coolant used to maintain proper temperature of the engine can be reduced by 11°C (20°F) because a significantly lower viscosity oil can be used with such change. The oil temperature can be reduced by at least 28°C (50°F), when coupled with the avoidance of tar deposit formation on the combustion chamber surfaces, and an increase in the compression ratio of the engine by at least one with the attendant improvement in fuel economy and power.
  • coated block in accordance with this invention, is the ability for resisting formic acid formation using flex fuels containing methanol.
  • flex fuels containing methanol typically, an engine would have its surfaces degrade at 32 000 km (20,000 miles) or greater as a result of the formation of formic acid under a peculiar set of engine conditions with such flex fuels.
  • the coated bore walls as herein, such resistance to formic acid corrosion is eliminated.
  • the coated product obtains greater accuracy of roundness within the cylinder bore as the conventional rings ride thereagainst, contributing to the reduction in blow-by as mentioned earlier.
  • the coated block plays an important role in the overall operation of engine efficiency.
  • the block has an interior cooling jacket 45 along its sides, and cooperates to receive a head 46 containing intake and exhaust passages 47, 48 opened and closed by intake and exhaust valves 49, 50 operated by a valve train 51 actuated by camshafts 52.
  • the combustible gases are ignited by spark ignition 53 located centrally of the combustion chamber 54 to move the piston 55, which in turn actuates a connecting rod 56 to turn a crankshaft 57 rotating within a crank case 58.
  • Oil is drawn from the crank case 58 and splashed within the interior of the block to lubricate and bathe the piston 55 during its reciprocal movement therein.
  • the cooling fluid circulates about the cylinder bore wall to extract heat therefrom, which influences the efficiency of the engine by reducing the heat input into the air/fuel charge during the intake stroke, and thus increases volumetric efficiency as well as power and fuel economy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Claims (15)

  1. Ein Beschichtungssystem aus Festschmierstoffen, das ein ölgeschmiertes Substrat (10) aus Leichtmetall oder Leichtmetallegierung umfaßt, das Gleitverschleiß bei hohen Temperaturen ausgesetzt ist und eine poröse Beschichtung besitzt, die eine Schicht (A) aus Körnern von agglomerierten Partikeln aus Festschmierstoff (15) und verschmolzenen Metallpartikeln (16) umfaßt, wobei diese Körner thermisch an diesem Substrat zum Haften gebracht werden,
    dadurch gekennzeichnet, daß diese Körner
    i) aus mindestens zwei verschiedenen ölanziehenden Festschmierstoffen, die aus der aus Graphit, Molybdändisulfid, Bornitrid, Calciumfluorid, Natriumfluorid und Lithiumfluorid bestehenden Reihe ausgewählt sind, und
    ii) aus gehärteten Partikeln eines an der Luft härtbaren Metalls bestehen, die als vernetzte Struktur (62) zusammengeschweißt sind und exponierte Kanten (61) besitzen.
  2. Ein Beschichtungssystem nach Anspruch 1, worin die Festschmierstoffe aus der aus Graphit, Molybdändisulfid, Bornitrid, Calciumfluorid und eutektischen Mischungen aus Lithiumfluorid mit Calciumfluorid oder Natriumfluorid bestehenden Reihe ausgewählt sind.
  3. Ein Beschichtungssystem nach Anspruch 1 oder 2, in dem dieses an der Luft härtende Metall Stahl ist.
  4. Ein Beschichtungssystem nach Anspruch 3, in dem diese Festschmierstoffpartikel 15-25 Volumenprozent und diese Stahlpartikel 74-85 Volumenprozent dieser Körner darstellen.
  5. Ein Beschichtungssystem nach Anspruch 3 oder 4, in dem dieser Stahl Edelstahl ist, der 15-24% Chrom und etwa 8% Nickel und als Rest Eisen enthält.
  6. Ein Beschichtungssystem nach Anspruch 3 oder 4, in dem dieser Stahl Edelstahl ist, der 8-20% Chrom, 2-8% Mangan und 8-16% Nickel enthält.
  7. Ein Beschichtungssystem nach Anspruch 3 oder 4, in dem dieser Stahl eine Stahllegierung ist, die 4-8% Mangan, 4-20% Chrom, 2-4% Nickel und 0,1-0,4% Kohlenstoff enthält.
  8. Ein Beschichtungssystem nach irgendeinem der vorhergehenden Ansprüche, worin das Substrat eine Wand (15; 18) einer Zylinderbohrung oder eines Zylindereinsatzes eines Verbrennungsmotors ist.
  9. Ein Verfahren zur Herstellung eines Beschichtungssystems aus Festschmierstoffen nach irgendeinem der vorhergehenden Ansprüche, das folgende Schritte umfaßt:
    a) Bildung von Körnern agglomerierter Partikel aus
    i) mindestens zwei verschiedenen ölanziehenden Festschmierstoffen, die aus der aus Graphit, Molybdändisulfid, Bornitrid, Calciumfluorid, Natriumfluorid und Lithiumfluorid bestehenden Reihe ausgewählt sind, und
    ii) einem schmelzbaren, an der Luft härtbaren Metall,
    wobei die Partikel in den Agglomeraten von einem niedrigschmelzenden, thermisch entfernbaren Medium zusammengehalten werden,
    b) Heißspritzen der Körner auf ein Substrat aus Leichtmetall oder Leichtmetallegierung in einem Dickenbereich von 100-250 µ, um das Medium im wesentlichen zu beseitigen und benachbarte Partikel miteinander zu verschmelzen, um eine poröse, anhaftende, vernetzte Struktur aus an der Luft härtbarem Metall um diese Festschmierstoffpartikel herum zu bilden,
    c) Beseitigung eines Teiles der verschmolzenen Partikel, um Kanten dieser verschmolzenen Partikel freizugeben, und
    d) Aussetzen der freigelegten Kanten dem Härten an der Luft.
  10. Ein Verfahren nach Anspruch 9, in dem das niedrigschmelzende Medium ein Wachs oder ein thermisch entfernbares thermoplastisches Polymer ist.
  11. Ein Verfahren nach Anspruch 9 oder Anspruch 10, in dem das Heißspritzen mittels Plasmaspritzen durchgeführt wird, um eine Beschichtung mit einer Porosität von 2-10% abzuscheiden.
  12. Ein Verfahren nach irgendeinem der Ansprüche 9 bis 11, in dem die Festschmierstoffpartikel und/oder die Partikel aus schmelzbarem Metall in den Körnern mit Nickel, Kobalt oder Kupfer verkapselt sind, und die an der Luft härtbare Legierung aus dem Verschmelzen der Partikel beim Heißspritzen resultiert.
  13. Ein Verfahren nach Anspruch 12, in dem die Körner ebenso harte Partikel einschließen und auch die harten Partikel verkapselt sind.
  14. Ein Verfahren nach irgendeinem der Ansprüche 9 bis 13, in dem diese Körner eine Partikelgröße im Bereich von 15-20 µ besitzen.
  15. Ein Verfahren nach irgendeinem der Ansprüche 9 bis 14, in dem Schritt (c) durch Ziehschleifen durchgeführt wird.
EP94918927A 1993-07-06 1994-06-24 Festschmierstoff und beschichtungssystem aus härtbarem stahl Expired - Lifetime EP0707620B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US88014 1993-07-06
US08/088,014 US5332422A (en) 1993-07-06 1993-07-06 Solid lubricant and hardenable steel coating system
PCT/GB1994/001366 WO1995002024A1 (en) 1993-07-06 1994-06-24 Solid lubricant and hardenable steel coating system

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Publication Number Publication Date
EP0707620A1 EP0707620A1 (de) 1996-04-24
EP0707620B1 true EP0707620B1 (de) 1997-12-29

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US (4) US5332422A (de)
EP (1) EP0707620B1 (de)
JP (1) JPH08512343A (de)
CA (1) CA2166182A1 (de)
DE (1) DE69407591T2 (de)
WO (1) WO1995002024A1 (de)

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US5302450A (en) * 1993-07-06 1994-04-12 Ford Motor Company Metal encapsulated solid lubricant coating system

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US5332422A (en) 1994-07-26
US5484662A (en) 1996-01-16
CA2166182A1 (en) 1995-01-19
DE69407591D1 (de) 1998-02-05
DE69407591T2 (de) 1998-04-16
US5408964A (en) 1995-04-25
WO1995002024A1 (en) 1995-01-19
EP0707620A1 (de) 1996-04-24
JPH08512343A (ja) 1996-12-24
US5464486A (en) 1995-11-07

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